Dynamic formation of SEBS copolymer submicrometric structures

Highly ordered A-B-A block copolymer arrangements in the submicrometric scale, resulting from dewetting and solvent evaporation of thin films, have inspired a variety of new applications in the nanometric world. Despite the progress observed in the control of such structures, the intricate scientific phenomena related to regular patterns formation are still not completely elucidated. SEBS is a standard example of a triblock copolymer that forms spontaneously impressive pattern arrangements. From macroscopic thin liquid films of SEBS solution, several physical effects and phenomena act synergistically to achieve well-arranged patterns of stripes and/or droplets. That is, concomitant with dewetting, solvent evaporation, and Marangoni effect, Rayleigh instability and phase separation also play important role in the pattern formation. These two last effects are difficult to be followed experimentally in the nanoscale, which render difficulties to the comprehension of the whole phenomenon. In this paper, we use computational methods for image analysis, which provide quantitative morphometric data of the patterns, specifically comprising stripes fragmentation into droplets. With the help of these computational techniques, we developed an explanation for the final part of the pattern formation, i.e. structural dynamics related to the stripes fragmentation. (C) 2010 Elsevier Ltd. All rights reserved.

Controlling the luminescence properties of poly(p-phenylene vinylene) entrapped in Langmuir and Langmuir-Blodgett films of stearic acid

Properties of hybrid films can be enhanced if their molecular architecture is controlled. In this paper, poly (p-phenylene vinylene) was mixed with stearic acid in order to form stable hybrid Langmuir monolayers. Surface properties of these films were investigated with measurements of surface pressure, and also with polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). The films were transferred from the air-water interface to solid supports through the Langmuir-Blodgett technique, and the viability of the film as optical device was investigated with fluorescence spectroscopy. Comparing the fluorescent spectra for the polymer in solution, as a casting film, and as an LB film, the emission bands for LB films were narrower and appeared at lower wavelengths. The interactions between the film components and the design for the LB film may take advantage of the method to immobilize luminescent polymers in mixed ultrathin films adsorbed in solid matrices. (C) 2011 Elsevier B.V. All rights reserved.

Quantification of Clay Dispersion in Nanocomposites of Styrenic Polymers

Polymer-clay nanocomposites are materials with many interesting structures, properties, and potential applications. Microstructural evaluation of a nanocomposite is not an easy task, as clay may form hierarchical structures which may look different when observed at various magnifications under a microscope, and also as the concepts of ""intercalation"" and ""exfoliation"" are not self-sufficient to describe its morphology. In this work polymer-clay nanocomposites of polystyrene and two styrene-containing block copolymers (styrene-butadiene-styrene and styrene-ethylene/butylene-styrene) were prepared using three different techniques. Clay dispersion was evaluated by a recently developed microscopy image analysis procedure, combining the analysis of optical and transmission electron micrographs, and the characterization was complemented by X-ray diffraction and rheological measurements. The results showed better clay dispersion for both block copolymers nanocomposites, mainly due to their molecular architectures. Moreover, the techniques which showed the best results involved mixing the materials in a solvent medium. POLYM. ENG. SCI., 50:257-267, 2010. (C) 2009 Society of Plastics Engineers

Biodegradable nanosize particles of poly(L,L-lactide)-b-poly(ethylene glycol)-b-poly(L,L-lactide)

Two series of poly(L,L-lactide-b-ethylene glycol-b-L,L-lactide) copolymers, PLA-PEO-PLA, were synthesized by polymerization Of L,L-lactide using a dihydroxy-terminated poly(ethylene glycol) (PEG) (M-n = 4000 or 600 g/mol) as coinitiator and stannous 2-ethylhexanoate, Sn(Oct)(2), as initiator. The synthesized copolymers have shown high stereoregularity as observed by C-13 NMR analyses. The nanoparticles were prepared by using a solvent diffusion method and the self-assemblage process and were characterized by NMR and SEM. It was possible to conclude that the self-assembled particles presented a core-shell structure characterized by a hydrophobic PLA core and a hydrophilic PEG shell, thus the NMR of the aqueous solutions indicated a quasi-solid behavior for the particles` interior. The diameters of the spherical particles as observed by SEM were in the 50-250 nm range, depending on the copolymer composition and the preparation procedure.

AN ASSESSMENT ON THE USE OF THE DEBYE-HUCKEL EQUATION FOR THE THERMODYNAMIC MODELING OF AQUEOUS SYSTEMS CONTAINING POLYMERS AND SALTS

In this work, a study on the role of the long-range term of excess Gibbs energy models in the modeling of aqueous systems containing polymers and salts is presented. Four different approaches on how to account for the presence of polymer in the long-range term were considered, and simulations were conducted considering aqueous solutions of three different salts. The analysis of water activity curves showed that, in all cases, a liquid-phase separation may be introduced by the sole presence of the polymer in the long-range term, regardless of how it is taken into account. The results lead to the conclusion that there is no single exact solution for this problem, and that any kind of approach may introduce inconsistencies.

Liquid-Liquid Equilibrium of Aqueous Two-Phase Systems Containing Some Synthetic Polyelectrolytes and Polyethylene Glycol

Experimental results are presented for the liquid-liquid equilibrium of aqueous two-phase systems containing a synthetic polyelectrolyte (polysodium acrylate, polysodium methacrylate, and polysodium ethylene sulfonate) and polyethylene glycol at (298.2 and 323.2) K. A total of 40 phase diagrams were obtained, comprising data both of the binodal curve (obtained through cloud-point measurements) and of equilibrium compositions. The influences of temperature, the nature of the polyelectrolyte monomer unit, and the chain length of both types of polymers are analyzed and discussed.

Influence of Pluronic (R) F68 on Ceftazidime Biological Activity in Parenteral Solutions

beta-Lactam antimicrobials are known to have a low concentration/therapeutic response. However, extending the period in which beta-lactam are free in the plasma does directly influence therapeutic outcomes. The objective of this study was to evaluate the influence of Pluronic (R) F68 on the antimicrobial activity of ceftazidime when admixed with aminophylline in parenteral solutions by the evaluation of its minimal inhibitory concentration (MIC) within 24 h. Ceftazidime, aminophylline, and Pluronics (R) F68 were evaluated using the MIC method against Escherichia coli and Pseudomonas aeruginosa, with these compounds individually and associated in the same parenteral solutions. When Pluronics (R) F68 was admixtured with ceftazidime alone or with ceftazidime and aminophylline, it was possible to observe lower MIC values not only at 24 h but also at 0 h for both microorganisms. This indicates that Pluronics (R) F68 may be able to enhance ceftazidime antimicrobial activity in the presence or absence of aminophylline. This fact suggests that Pluronics (R) F68 can be applied to allow the administration of ceftazidime under continuous infusion in parenteral solutions, beneficiating hospital pharmacotherapy. It may also be possible to reduce ceftazidime doses in formulations achieving the same therapeutic results. (C) 2010 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 100:715-720, 2011

Interaction of adrenocorticotropin peptides with microheterogeneous systems - A fluorescence study

Adrenocorticotropin (ACM) and alpha-melanocyte stimulating hormone (alpha-MSH) are peptides which present many physiological effects related to pigmentation, motor and sexual behavior, learning and memory, analgesia, anti-inflammatory and antipyretic processes. The 13 amino acid residues of alpha-MSH are the same initial sequence of ACM and due to the presence of a tryptophan residue in position 9 of the peptide chain, fluorescence techniques could be used to investigate the conformational properties of the hormones in different environments and the mechanisms of interaction with biomimetic systems like sodium dodecyl sulphate (SDS) micelles, sodium dodecyl sulphate-poly(ethylene oxide) (SDS-PEO) aggregates and neutral polymeric micelles. In buffer solution, fluorescence parameters were typical of peptides containing tryptophan exposed to the aqueous medium and upon addition of surfactant and polymer molecules, the gradual change of those parameters demonstrated the interaction of the peptides with the microheterogeneous systems. From time-resolved experiments it was shown that the interaction proceeded with conformational changes in both peptides, and further information was obtained from quenching of Trp fluorescence by a family of N-alkylpyridinium ions, which possess affinity to the microheterogeneous systems dependent on the length of the alkyl chain. The quenching of Trp fluorescence was enhanced in the presence of charged micelles, compared to the buffer solution and the accessibility of the fluorophore to the quencher was dependent on the peptide and the alkylpyridinium: in ACTH(1-21) highest collisional constants were obtained using ethylpyridinium as quencher, indicating a location of the residue in the surface of the micelle, while in alpha-MSH the best quencher was hexylpyridinium, indicating insertion of the residue into the non-polar region of the micelles. The results had shown that the interaction between the peptides and the biomimetic systems where driven by combined electrostatic and hydrophobic effects: in ACTH(1-24) the electrostatic interaction between highly positively charged C-terminal and negatively charged surface of micelles; and aggregates predominates over hydrophobic interactions involving residues in the central region of the peptide; in alpha-MSH, which presents one residual positive charge, the hydrophobic interactions are relevant to position the Trp residue in the non-polar region of the microheterogeneous systems. (C) 2008 Elsevier B.V. All rights reserved.

Demixing instability in coil-rod blends undergoing polycondensation reactions

The authors extend their earlier work on the stability of a reacting binary polymer blend with respect to demixing [D. J. Read, Macromolecules 31, 899 (1998); P. I. C. Teixeira , Macromolecules 33, 387 (2000)] to the case where one of the polymers is rod-like and may order nematically. As before, the authors combine the random phase approximation for the free energy with a Markov chain model for the chemistry to obtain the spinodal as a function of the relevant degrees of reaction. These are then calculated by assuming a simple second-order chemical kinetics. Results are presented, for linear systems, which illustrate the effects of varying the proportion of coils and rods, their relative sizes, and the strength of the nematic interaction between the rods. (c) 2007 American Institute of Physics.

PEG-b-PPS diblock copolymer aggregates for hydrophobic drug solubilization and release: cyclosporin A as an example

Micelles formed from amphiphilic block copolymers have been explored in recent years as carriers for hydrophobic drugs. In an aqueous environment, the hydrophobic blocks form the core of the micelle, which can host lipophilic drugs, while the hydrophilic blocks form the corona or outer shell and stabilize the interface between the hydrophobic core and the external medium. In the present work, mesophase behavior and drug encapsulation were explored in the AB block copolymeric amphiphile composed of poly(ethylene glycol) (PEG) as a hydrophile and poly(propylene sulfide) PPS as a hydrophobe, using the immunosuppressive drug cyclosporin A (CsA) as an example of a highly hydrophobic drug. Block copolymers with a degree of polymerization of 44 on the PEG and of 10, 20 and 40 on the PPS respectively (abbreviated as PEG44-b-PPS10, PEG44-b-PPS20, PEG44-b-PPS40) were synthesized and characterized. Drug-loaded polymeric micelles were obtained by the cosolvent displacement method as well as the remarkably simple method of dispersing the warm polymer melt, with drug dissolved therein, in warm water. Effective drug solubility up to 2 mg/mL in aqueous media was facilitated by the PEG- b-PPS micelles, with loading levels up to 19% w/w being achieved. Release was burst-free and sustained over periods of 9-12 days. These micelles demonstrate interesting solubilization characteristics, due to the low glass transition temperature, highly hydrophobic nature, and good solvent properties of the PPS block

Beneficial Effects of Selected Additives on Asphalt Cement Mixes, HR-278, 1987

Effects of polyolefins, neoprene, styrene-butadiene-styrene (SBS) block copolymers, styrene-butadiene rubber (SBR) latex, and hydrated lime on two asphalt cements were evaluated. Physical and chemical tests were performed on a total of 16 binder blends. Asphalt concrete mixes were prepared and tested with these modified binders and two aggregates (crushed limestone and gravel), each at three asphalt content levels. Properties evaluated on the modified binders (original and thin-film oven aged) included: viscosity at 25 deg C, 60 deg C and 135 deg C with capillary tube and cone-plate viscometer, penetration at 5 deg C and 25 deg C, softening point, force ductility, and elastic recovery at 10 deg C, dropping ball test, tensile strength, and toughness and tenacity tests at 25 deg C. From these the penetration index, the viscosity-temperature susceptibility, the penetration-viscosity number, the critical low-temperature, long loading-time stiffness, and the cracking temperature were calculated. In addition, the binders were studied with x-ray diffraction, reflected fluorescence microscopy, and high-performance liquid chromatography techniques. Engineering properties evaluated on the 72 asphalt concrete mixes containing additives included: Marshall stability and flow, Marshall stiffness, voids properties, resilient modulus, indirect tensile strength, permanent deformation (creep), and effects of moisture by vacuum-saturation and Lottman treatments. Pavement sections of varied asphalt concrete thicknesses and containing different additives were compared to control mixes in terms of structural responses and pavement lives for different subgrades. Although all of the additives tested improved at least one aspect of the binder/mixture properties, no additive was found to improve all the relevant binder/mixture properties at the same time. On the basis of overall considerations, the optimum beneficial effects can be expected when the additives are used in conjunction with softer grade asphalts.

Development of Bio-Based Polymers for Use in Asphalt, TR-639, 2014

Asphalt binder is typically modified with poly type (styrene-butadiene-styrene or SBS) polymers to improve its rheological properties and performance grade. The elastic and principal component of SBS polymers is butadiene. For the last decade, butadiene prices have fluctuated and significantly increased, leading state highway agencies to search for economically viable alternatives to butadiene based materials. This project reports the recent advances in polymerization techniques that have enabled the synthesis of elastomeric, thermoplastic, block-copolymers (BCPs) comprised of styrene and soybean oil, where the “B” block in SBS polymers is replaced with polymerized triglycerides derived from soybean oil. These new breeds of biopolymers have elastomeric properties comparable to well-established butadiene-based styrenic BCPs. In this report, two types of biopolymer formulations are evaluated for their ability to modify asphalt binder. Laboratory blends of asphalt modified with the biopolymers are tested for their rheological properties and performance grade. Blends of asphalt modified with the biopolymers are compared to blends of asphalt modified with two commonly used commercial polymers. The viscoelastic properties of the blends show that biopolymers improve the performance grade of the asphalt to a similar and even greater extent as the commercial SBS polymers. Results shown in this report indicate there is an excellent potential for the future of these biopolymers as economically and environmentally favorable alternatives to their petrochemically-derived analogs.

Uusien polyuretaanimateriaalien kehittäminen

Polyuretaanielastomeerit ovat jaksottaisia sekapolymeerejä, jotka muodostuvat vuoroittaisista joustavien ketjujen segmenteistä ja hyvin polaarisista kovista segmenteistä. Kemiallinen rakenne ja ominaisuudet riippuvat käytetyistä reaktiokomponenteista. Pehmeän segmentin muodostaa polyoli ja kovan segmentin muodostaa yleensä di-isosyanaatti ja ketjunjatkaja. Polyuretaanielastomeerien valmistus tapahtuu valamalla, jolloin reaktiokomponentit ovat nestemäisiä. Työssä tutkittiin kahta perusmateriaalia ja yhden lisäaineen vaikutusta niiden ominaisuuksiin. Erityisesti kiinnitettiin huomiota dynaamisiin ja mekaanisiin ominaisuuksiin ja verrattiin aineita keskenään. Käytettyjä karakterisointimenetelmiä olivat kontaktikulmamittaukset, DMTA-mittaukset, dynaaminen rasittaminen pyörityslaitteella, elektronimikroskopia, hydrolyysitesti, vetotesti ja kulutustesti. Tutkittujen materiaalien pääasiallinen käyttökohde on pyörä- tai telapinnoitteena. Työn aikana kehitettiin pyörityslaite, jolla voitiin tutkia pinnoitemateriaalin käyttäytymistä halutuissa rasitusolosuhteissa. Lisäaineen vaikutus dynaamisiin ominaisuuksiin oli negatiivinen tai olematon, sillä DMTA-testien perusteella lisäaine kasvatti materiaalien häviötekijää (tan d). Pyöritystestien perusteella lisäaineella ei ollut vaikutusta hystereesiin eli pinnoitemateriaalin lämpenemiseen testin aikana. Uusi tutkittu materiaali osoittautui dynaamisissa kokeissa paremmaksi kuin vanha tuotantomateriaali. Lisäaine kasvatti molempien tutkittujen aineiden pintaenergiaa kontaktikulmamittausten perusteella. Tuotantoaineen vetomurtolujuus kasvoi lisäaineen vaikutuksesta, mutta uuden aineen vetomurtolujuus pieneni. Lisäaineella oli lievä hydrolyysiltä suojaava vaikutus tutkituilla perusaineilla. Uusi tutkittu perusmateriaali sieti hydrolyysiä paremmin kuin tuotantomateriaali, koska sen valmistuksessa käytettiin polyeetteripolyolia ja tuotantomateriaalissa polyesteripolyolia.

Interação tensoativo/hidrótropo em sistemas aquosos, utilizando ressonância magnética nuclear de ¹H e 13C

In this work, it was studied the behavior of the nonionic surfactant aqueous solutions, containing or not a hydrotropic agent, by resonance magnetic nuclear (NMR). We have studied monofunctional diblock copolymers of poly(propylene oxide-ethylene oxide) (R-PPO-PEO-OH, where R length is linear C4) as nonionic surfactant and sodium p-toluenesulfonate (NaPTS) as hydrotropic agent. The critical micelle concentration (CMC) of the aqueous copolymer solution was obtained from ¹H-NMR. The preliminary study of the interaction between the copolymer, under the unimer and micelle forms, and the hydrotrope, in aqueous solutions, was evaluated by ¹H-NMR and 13C-NMR.

Síntese e caracterização de dispersões aquosas de poliuretanos à base de copolímeros em bloco de poli(glicol etilênico) e poli(glicol propilênico)

Non-polluting polyurethane aqueous dispersions, with 40% of solids content, were synthesized based on block copolymers of poly(ethylene glycol) and poly(propylene glycol) (PEG-b-PPG), with PEG hydrophilic segments content of 7 and 25%, poly(propylene glycol) (PPG), dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI), and hydrazine. Different formulations were synthesized by varying the equivalent-grams ratios between isocyanate and hydroxyl groups (NCO/OH) and PPG and (PEG-b-PPG). The presence of high amounts of PEG in the formulations provoked the formation of gels. Average particle size and viscosity of the dispersions were determined. Mechanical properties and water absorption resistance of cast films were evaluated.